JPH06176800A - Temperature difference battery - Google Patents
Temperature difference batteryInfo
- Publication number
- JPH06176800A JPH06176800A JP43A JP35176292A JPH06176800A JP H06176800 A JPH06176800 A JP H06176800A JP 43 A JP43 A JP 43A JP 35176292 A JP35176292 A JP 35176292A JP H06176800 A JPH06176800 A JP H06176800A
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- temperature difference
- redox
- electromotive force
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は温度差電池、さらに詳細
には熱を直接電気に変える熱電変換器としての電気化学
的な温度差電池に関するものである。特に、排熱利用お
よびコージェネレーション用途に有効な温度差電池に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a temperature difference battery, and more particularly to an electrochemical temperature difference battery as a thermoelectric converter that directly converts heat into electricity. In particular, the present invention relates to a temperature difference battery which is effective for utilization of waste heat and cogeneration.
【０００２】[0002]
【従来の技術】従来、熱を直接電気に変える熱電変換器
として電気化学的な温度差電池が知られている。この温
度差電池は、高低温電極間に酸化還元電位が温度によっ
て変化するレドックス対イオンを含む電解質水溶液を満
たすことにより、両電極間に電位差を生じさせるもので
ある。これまでレドックス対イオンとして例えば［Ｆｅ
（ＣＮ）6］3-および［Ｆｅ（ＣＮ）6］4-が知られてお
り、このレドックス対イオンにおいては、高温電極が
負、低温電極が正となる電位差を生じ、高低温電極では
それぞれ以下の反応が進行する。2. Description of the Related Art Conventionally, an electrochemical temperature difference battery is known as a thermoelectric converter that directly converts heat into electricity. In this temperature difference battery, a high-low temperature electrode is filled with an aqueous electrolyte solution containing a redox counter ion whose redox potential changes with temperature, thereby causing a potential difference between both electrodes. So far, for example, [Fe
(CN) 6 ] 3− and [Fe (CN) 6 ] 4− are known, and in this redox counterion, a potential difference is generated in which the high temperature electrode is negative and the low temperature electrode is positive. The following reactions proceed.
【０００３】低温電極［Ｆｅ（ＣＮ）6］3-＋ｅ-→［Ｆ
ｅ（ＣＮ）6］4- [0003] low-temperature electrode [Fe (CN) 6] 3- + e - → [F
e (CN) 6 ] 4-
【０００４】高温電極［Ｆｅ（ＣＮ）6］4-→［Ｆｅ
（ＣＮ）6］3-＋ｅ- High temperature electrode [Fe (CN) 6 ] 4- → [Fe
(CN) 6] 3- + e -
【０００５】ここで低温電極で生成した［Ｆｅ（ＣＮ）
6］4-は高温電極へ、高温電極で生成した［Ｆｅ（Ｃ
Ｎ）6］3-は低温電極へ、拡散対流により循環し、無動
力で定常的に発電させていた。[Fe (CN) produced at the low temperature electrode here.
6 ] 4− is generated at the high temperature electrode and [Fe (C
N) 6 ] 3− circulated to the low temperature electrode by diffusive convection, and generated power without power.
【０００６】このような温度差電池では、レドックス対
イオンの酸化還元電位が温度によってできるだけ大きく
変化するものが好ましく、同じ温度差において高起電力
化が可能となる。これまで最も酸化還元電位が温度によ
って大きく変化するレドックス対として［Ｆｅ（ＣＮ）
6］3-／［Ｆｅ（ＣＮ）6］4-系レドックス対が知られて
おり、温度差９０℃のとき、起電力は１２６ｍＶ（１．
４Ｖ／℃）であった。この温度差電池系では、レドック
ス対を溶解させるための溶媒に水を用いていることか
ら、１００℃以上になると高温側電極温度の上昇ととも
に電池セル内の圧力が急激に増大し、上記温度差以上を
高低温電極間に付けることは困難であった。したがっ
て、このような温度差電池の性能を向上させるために
は、さらに酸化還元電位が温度によって大きく変化する
レドックス対を用い単位温度差あたりの起電力を大きく
し、溶解性の高い沸点溶媒を用い、高温度差によりさら
に高起電力化を図ることが望まれていた。[0006] In such a temperature difference battery, it is preferable that the redox potential of the redox counter ion changes as much as possible depending on the temperature, and high electromotive force can be achieved at the same temperature difference. So far, [Fe (CN) has been used as a redox couple whose redox potential varies greatly with temperature.
6 ] 3− / [Fe (CN) 6 ] 4− system redox pair is known, and the electromotive force is 126 mV (1.
4 V / ° C). In this temperature difference battery system, since water is used as the solvent for dissolving the redox couple, the pressure inside the battery cell rapidly increases as the temperature of the electrode on the high temperature side rises at 100 ° C. or higher, and It was difficult to attach the above between the high and low temperature electrodes. Therefore, in order to improve the performance of such a temperature difference battery, a redox couple whose redox potential greatly changes depending on temperature is used to increase the electromotive force per unit temperature difference, and a boiling point solvent with high solubility is used. It has been desired to further increase the electromotive force due to the high temperature difference.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、従来の温度
差電池では、レドックス対の酸化還元電位の温度依存性
が小さく、９０℃以上の温度差を付けることができなく
起電力が小さいという問題点を解決するため、酸化還元
電位の温度依存性が大きいレドックス対イオンを用い、
さらにこれを溶解させるための水より沸点の高い有機溶
媒を用いることにより、９０℃以上の温度差を付けるこ
とを可能とし、高起電力化を可能にさせた温度差電池を
提供するものである。SUMMARY OF THE INVENTION According to the present invention, the conventional temperature difference battery has a small temperature dependence of the redox potential of the redox pair, cannot make a temperature difference of 90 ° C. or more, and has a small electromotive force. In order to solve the problem, we used a redox counterion whose temperature dependence of the redox potential is large,
Further, by using an organic solvent having a boiling point higher than that of water for dissolving this, it is possible to provide a temperature difference of 90 ° C. or more, and to provide a temperature difference battery capable of increasing electromotive force. .
【０００８】[0008]
【課題を解決するための手段】本発明は上記課題を解決
するため、温度の異なる高温側電極および低温側電極間
に、酸化還元電位が温度によって変化するレドックス対
系電解質およびそれを溶解させるための溶媒を有する温
度差電池において、前記溶媒がベンゾニトリルであるこ
とを特徴とする温度差電池である。In order to solve the above-mentioned problems, the present invention is intended to dissolve a redox pair system electrolyte whose redox potential varies with temperature and an electrode between a high temperature side electrode and a low temperature side electrode having different temperatures. In the temperature difference battery having the solvent, the solvent is benzonitrile.
【０００９】また、レドックス対系電解質がＦｅＢ
ｒ2，ＦｅＢｒ3またはＣｕＢｒ，ＣｕＢｒ2であること
を特徴とし、さらに詳細に述べれば、本発明の温度差電
池は、単位温度差あたりの起電力を大きくできるレドッ
クス対イオン、およびこれを溶解させるための溶媒に高
沸点の有機溶媒を用いることにより、高起電力化させた
ことを特徴とする。Further, the redox electrolyte is FeB.
r 2 , FeBr 3 or CuBr, CuBr 2 , and more specifically, the temperature difference battery of the present invention has a redox counter ion capable of increasing an electromotive force per unit temperature difference, and a redox counter ion for dissolving the same. A high boiling point organic solvent is used as a solvent for the purpose of increasing the electromotive force.
【００１０】本発明におけるベンゾニトリル有機溶媒を
用いることにより、高温側電極温度をベンゾニトリルの
沸点１９１．１０℃付近まで上昇させることができるの
で、両電極間の温度差を従来の９０℃より大きく付ける
ことが可能となり、従来の温度差電池にはない、極めて
大きな起電力を発現させることができる。By using the benzonitrile organic solvent in the present invention, the temperature of the electrode on the high temperature side can be raised up to the boiling point of benzonitrile of 191.10 ° C., so that the temperature difference between both electrodes is larger than the conventional temperature of 90 ° C. Therefore, it is possible to develop an extremely large electromotive force which is not present in the conventional temperature difference battery.
【００１１】以下の本発明を詳細に説明する。The present invention will be described in detail below.
【００１２】本発明者らは、水に比べ沸点の高い各種溶
媒を用い、レドックス対の溶解性と温度差間における起
電力値について鋭意実験を重ねた結果、レドックス対系
電解質としてＦｅＢｒ2，ＦｅＢｒ3またはＣｕＢｒ，Ｃ
ｕＢｒ2を、またその溶媒としてベンゾニトリルを用い
ることにより、レドックス対系電解質の高い溶解性と高
起電力を発現することを見いだした。The present inventors conducted various experiments on the solubility of the redox couple and the electromotive force value between the temperature differences using various solvents having a higher boiling point than water. As a result, FeBr 2 and FeBr were used as the redox couple system electrolyte. 3 or CuBr, C
It was found that by using uBr 2 and benzonitrile as a solvent thereof, high solubility and high electromotive force of the redox couple system electrolyte are exhibited.
【００１３】本発明において、レドックス対系電解質の
溶媒に用いられるベンゾニトリル有機溶媒は、室温でＦ
ｅＢｒ2およびＦｅＢｒ3を約０．５ｍｏｌ／ｌ、ＣｕＢ
ｒおよびＣｕＢｒ2を約０．１ｍｏｌ／ｌ溶解させるこ
とができ、ベンゾニトリルの沸点である１９１．１０℃
近くまでレドックス対の熱分解等も起こらず良好な溶解
性を示す。また、単位温度差あたりの起電力は、電解液
の濃度が０．１ｍｏｌ／ｌ以上であればほぼ一定の値
２．０ｍＶ／℃であり、従来の［Ｆｅ（ＣＮ）6］3-／
［Ｆｅ（ＣＮ）6］4-系に比べ、約１．７倍の値が得ら
れる。In the present invention, the benzonitrile organic solvent used as the solvent for the redox couple electrolyte is F 2 at room temperature.
About 0.5 mol / l of eBr 2 and FeBr 3 , CuB
r and CuBr 2 can be dissolved in about 0.1 mol / l, and the boiling point of benzonitrile is 191.10 ° C.
Good solubility is exhibited up to the vicinity without thermal decomposition of the redox couple. Further, the electromotive force per unit temperature difference is a substantially constant value of 2.0 mV / ° C when the concentration of the electrolytic solution is 0.1 mol / l or more, which is the same as that of the conventional [Fe (CN) 6 ] 3- /
The value is about 1.7 times that of the [Fe (CN) 6 ] 4− system.
【００１４】このようなレドックス型温度差電池では、
単位温度差あたりの起電力は電極で起こるレドックス対
の酸化還元反応に伴うエントロピー変化に大きく依存す
ることが知られているが、特にＦｅＢｒ2，ＦｅＢｒ3ま
たはＣｕＢｒ，ＣｕＢｒ2は酸化還元反応に伴うベンゾ
ニトリルとの溶媒和の変化が大きく、エントロピーも大
きく変化するため、高起電力を発現すると考えられる。In such a redox type temperature difference battery,
It is known that the electromotive force per unit temperature difference largely depends on the entropy change accompanying the redox reaction of the redox pair occurring at the electrode. Especially, FeBr 2 , FeBr 3 or CuBr, CuBr 2 are involved in the redox reaction. It is considered that a high electromotive force is exhibited because the solvation with benzonitrile changes greatly and the entropy also changes greatly.
【００１５】[0015]
【実施例】次に本発明を実施例により、さらに具体的に
説明する。EXAMPLES Next, the present invention will be described more specifically by way of examples.
【００１６】図１に示すように２枚の白金電極（縦２０
ｍｍ、横７ｍｍ、厚さ１００μｍ）Ｅ1、Ｅ2の間にベン
ゾニトリルを溶媒に用いた０．１ｍｏｌ／ｌのＦｅＢｒ
2およびＦｅＢｒ3溶液１を満たし、密閉固定した。さら
に電極間に電流計および電圧計を接続させた。この温度
差電池を高温熱源２、低温熱源３の間に設置し、電極Ｅ
1、Ｅ2間に温度差を与えたところ、電極Ｅ1温度１２７
℃、電極Ｅ2温度２０℃、電極間温度差１０７℃のと
き、約２２０ｍＶの開放起電力と約１８０ｍＡの短絡電
流が得られた。As shown in FIG. 1, two platinum electrodes (length 20) are used.
mm, width 7 mm, thickness 100 μm) 0.1 mol / l FeBr using benzonitrile as a solvent between E 1 and E 2.
2 and FeBr 3 solution 1 were filled and hermetically fixed. Further, an ammeter and a voltmeter were connected between the electrodes. This temperature difference battery is installed between the high temperature heat source 2 and the low temperature heat source 3, and the electrode E
When a temperature difference was applied between 1 and E 2 , the temperature of the electrode E 1 was 127
When the temperature was 20 ° C., the temperature of the electrode E 2 was 20 ° C., and the temperature difference between the electrodes was 107 ° C., an open electromotive force of about 220 mV and a short circuit current of about 180 mA were obtained.
【００１７】同様にベンゾニトリルを溶媒に用いた０．
１ｍｏｌ／ｌのＣｕＢｒおよびＣｕＢｒ2溶液ｌを満た
し、電極Ｅ1、Ｅ2間に温度差を与えたところ、電極Ｅ1
温度１３０℃、電極Ｅ2温度２５℃、電極間温度差１０
５℃のとき、約２１３ｍＶの開放起電力と約１６５ｍＡ
の短絡電流が得られた。Similarly, using benzonitrile as a solvent,
When 1 mol / l of CuBr and CuBr 2 solution 1 was filled and a temperature difference was given between electrodes E 1 and E 2 , electrode E 1
Temperature 130 ° C, electrode E 2 temperature 25 ° C, temperature difference between electrodes 10
Open electromotive force of about 213 mV and about 165 mA at 5 ° C
The short circuit current of was obtained.
【００１８】以上の結果より、本発明による温度差電池
は、水より高い沸点を有する有機溶媒を用いることによ
り、従来の温度差電池ではできなかった電極間温度差１
００℃以上を達成し、さらに約１．７倍の単位温度差あ
たり起電力の向上が認められた。From the above results, the temperature difference battery according to the present invention uses an organic solvent having a boiling point higher than that of water.
A temperature of 00 ° C. or higher was achieved, and an improvement in electromotive force per unit temperature difference of about 1.7 times was observed.
【００１９】[0019]
【発明の効果】本発明によれば、単位温度差あたりの起
電力の大きいレドックス対−高沸点溶媒系を用いること
により、高温側電極温度を１００℃以上に設定でき、レ
ドックス対の酸化還元電位を容易に増大させることが可
能となる。つまり、電池の起電力の増大を可能にでき
る。本発明の温度差電池は排熱利用およびコージェネレ
ーション用途として極めて有効である。According to the present invention, by using a redox couple-high boiling point solvent system having a large electromotive force per unit temperature difference, the high temperature side electrode temperature can be set to 100 ° C. or higher, and the redox potential of the redox couple can be set. Can be easily increased. That is, the electromotive force of the battery can be increased. The temperature difference battery of the present invention is extremely effective for utilization of exhaust heat and for cogeneration.
【図１】本発明の温度差電池の一構成例を示す概念図。FIG. 1 is a conceptual diagram showing a configuration example of a temperature difference battery of the present invention.
１ ベンゾニトリル溶液 ２ 高温熱源 ３ 低温熱源 1 Benzonitrile solution 2 High temperature heat source 3 Low temperature heat source
Claims (3)
間に、酸化還元電位が温度によって変化するレドックス
対系電解質およびそれを溶解させるための溶媒を有する
温度差電池において、前記溶媒がベンゾニトリルである
ことを特徴とする温度差電池。1. A temperature difference battery comprising a redox pair electrolyte having a redox potential varying with temperature and a solvent for dissolving the redox electrolyte between a high temperature electrode and a low temperature electrode having different temperatures, wherein the solvent is benzonitrile. Is a temperature difference battery.
ＦｅＢｒ3であることを特徴とする請求項１記載の温度
差電池。2. The redox couple electrolyte is FeBr 2 ,
The temperature difference battery according to claim 1, which is FeBr 3 .
ｕＢｒ2であることを特徴とする請求項１記載の温度差
電池。3. The redox couple electrolyte is CuBr, C.
The temperature difference battery according to claim 1, wherein the temperature difference battery is uBr 2 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35176292A JP3191831B2 (en) | 1992-12-08 | 1992-12-08 | Temperature difference battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35176292A JP3191831B2 (en) | 1992-12-08 | 1992-12-08 | Temperature difference battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06176800A true JPH06176800A (en) | 1994-06-24 |
| JP3191831B2 JP3191831B2 (en) | 2001-07-23 |
Family
ID=18419440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35176292A Expired - Fee Related JP3191831B2 (en) | 1992-12-08 | 1992-12-08 | Temperature difference battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3191831B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012510555A (en) * | 2008-12-03 | 2012-05-10 | クアンタム エナジー リサーチ センター | Phase change material, method for producing the same, and method for producing module using phase change material |
| CN106532095A (en) * | 2016-10-12 | 2017-03-22 | 中国工程物理研究院化工材料研究所 | High-power-density electrolyte thermobattery and preparation method for porous carbon electrodes |
-
1992
- 1992-12-08 JP JP35176292A patent/JP3191831B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012510555A (en) * | 2008-12-03 | 2012-05-10 | クアンタム エナジー リサーチ センター | Phase change material, method for producing the same, and method for producing module using phase change material |
| CN106532095A (en) * | 2016-10-12 | 2017-03-22 | 中国工程物理研究院化工材料研究所 | High-power-density electrolyte thermobattery and preparation method for porous carbon electrodes |
| CN106532095B (en) * | 2016-10-12 | 2019-03-22 | 中国工程物理研究院化工材料研究所 | The electrolyte thermoelectric cell of high power density and the preparation method of porous carbon electrodes |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3191831B2 (en) | 2001-07-23 |
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